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Ultraviolet radiation is the key factor driving tropospheric photochemistry. It is strongly modulated by clouds and aerosols. A quantitative understanding of the radiation field and its effect on photochemistry is thus only possible with a detailed knowledge of the interaction between clouds and radiation. The overall objective of the project INSPECTRO was the characterization of the three-dimensional actinic radiation field under cloudy conditions. This was achieved during two measurement campaigns in Norfolk (East Anglia, UK) and Lower Bavaria (Germany) combining space-based, aircraft and ground-based measurements as well as simulations with the one-dimensional radiation transfer model UVSPEC and the three-dimensional radiation transfer model MYSTIC. <br><br> During both campaigns the spectral actinic flux density was measured at several locations at ground level and in the air by up to four different aircraft. This allows the comparison of measured and simulated actinic radiation profiles. In addition satellite data were used to complete the information of the three dimensional input data set for the simulation. A three-dimensional simulation of actinic flux density data under cloudy sky conditions requires a realistic simulation of the cloud field to be used as an input for the 3-D radiation transfer model calculations. Two different approaches were applied, to derive high- and low-resolution data sets, with a grid resolution of about 100 m and 1 km, respectively. <br><br> The results of the measured and simulated radiation profiles as well as the results of the ground based measurements are presented in terms of photolysis rate profiles for ozone and nitrogen dioxide. During both campaigns all spectroradiometer systems agreed within ±10% if mandatory corrections e.g. stray light correction were applied. Stability changes of the systems were below 5% over the 4 week campaign periods and negligible over a few days. The J(O<sup>1</sup>D) data of the single monochromator systems can be evaluated for zenith angles less than 70°, which was satisfied by nearly all airborne measurements during both campaigns. The comparison of the airborne measurements with corresponding simulations is presented for the total, downward and upward flux during selected clear sky periods of both campaigns. The compliance between the measured (from three aircraft) and simulated downward and total flux profiles lies in the range of ±15%.
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The first three Canadian Arctic ACE validation campaigns were held during polar sunrise at Eureka, Nunavut, Canada (80° N, 86° W) from 2004 to 2006 in support of validation of the ACE (Atmospheric Chemistry Experiment) satellite mission. Three or four zenith-sky viewing UV-visible spectrometers have taken part in each of the three campaigns. The differential slant column densities and vertical column densities of ozone and NO<sub>2</sub> from these instruments have been compared following the methods of the UV-visible Working Group of the NDACC (Network for Detection of Atmospheric Composition Change). The instruments are found to partially agree within the required accuracies for both species, although both the vertical and slant column densities are more scattered than required. This might be expected given the spatial and temporal variability of the Arctic stratosphere in spring. The vertical column densities are also compared to integrated total columns from ozonesondes and integrated partial columns from the ACE-FTS (ACE-Fourier Transform Spectrometer) and ACE-MAESTRO (ACE-Measurements of Aerosol Extinction in the Stratosphere and Troposphere Retrieved by Occultation) instruments on board ACE. For both species, the columns from the ground-based instruments and the ozonesondes are found to generally agree within their combined error bars. The ACE-FTS ozone partial columns and the ground-based total columns agree within 4.5%, averaged over the three campaigns. The ACE-MAESTRO ozone partial columns are generally smaller than those of the ground-based instruments, by an average of 9.9%, and are smaller than the ACE-FTS columns by an average of 14.4%. The ACE-FTS NO<sub>2</sub> partial columns are an average of 13.4% smaller than the total columns from the ground-based instruments, as expected. The ACE-MAESTRO NO<sub>2</sub> partial columns are larger than the total columns of the ground-based instruments by an average of 2.5% and are larger than the partial columns of the ACE-FTS by an average of 15.5%.
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During the National Aeronautics and Space Administration (NASA) Intercontinental Chemical Transport Experiment, Phase B (INTEX-B), in the spring of 2006, airborne measurements were made in the United States Pacific Northwest of the major inorganic ions and the water-soluble organic carbon (WSOC) of submicron (PM<sub>1.0</sub>) aerosol. An atmospheric trajectory (HYSPLIT) and a Lagrangian particle dispersion model (Flexpart) quantifying source contributions for carbon monoxide (CO) were used to segregate air masses into those of primarily Asian influence (>75% Asian CO) or North American influence (>75% North American CO). Of the measured compounds, fine particle mass mostly consisted of water-soluble organic carbon and sulfate, with median sulfate and WSOC concentrations in two to four times higher, respectively, in North American air masses versus transported Asian air masses. The fraction of WSOC to sulfate in transported Asian air masses was significantly lower than one at altitudes above 3 km due to depleted organic aerosol, opposite to what has been observed closer to Asia and in the northeastern United States, where organic components were at higher concentrations than sulfate in the free troposphere. The observations could be explained by loss of sulfate and organic aerosol by precipitation scavenging, with reformation of mainly sulfate during advection from Asia to North America. In contrast to free tropospheric measurements, for all air masses below approximately 2 km altitude median WSOC-sulfate ratios were consistently between one and two. WSOC sources were investigated by multivariate linear regression analyses of WSOC and volatile organic compounds (VOCs). In Asian air masses, of the WSOC variability that could be explained (49%), most was related to fossil fuel combustion VOCs, compared to North American air masses, where 75% of the WSOC variability was explained through a nearly equal combination of fossil fuel combustion and biogenic VOCs. Distinct WSOC plumes encountered during the experiment were also studied. A plume observed near the California Central Valley at 0.6 km altitude was related to both fossil fuel combustion and biogenic VOCs. Another Central Valley plume observed over Nevada at 3 to 5 km, in a region of cloud detrainment, was mostly related to biogenic VOCs.
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The hygroscopic growth and activation of two HULIS (HUmic LIke Substance) and one Aerosol-Water-Extract sample, prepared from urban-type aerosol, were investigated. All samples were extracted from filters, redissolved in water and atomized for the investigations presented here. The hygroscopic growth measurements were done using LACIS (Leipzig Aerosol Cloud Interaction Simulator) together with a HH-TDMA (High Humidity Tandem Differential Mobility Analyzer). Hygroscopic growth was determined for relative humidities (RHs) up to 99.75%. The critical diameters for activation were measured for supersaturations between 0.2 and 1%. All three samples showed a similar hygroscopic growth behavior, and the two HULIS samples also were similar in their activation behavior, while the Aerosol-Water-Extract turned out to be more CCN active than the HULIS samples. The experimental data was used to derive parameterizations for the hygroscopic growth and activation of HULIS particles. The concept of ρ<sub>ion</sub> (Wex et al., 2007a) and the Szyszkowski-equation (Szyszkowski, 1908; Facchini, 1999) were used for parameterizing the Raoult and the Kelvin (surface tension) terms of the Köhler equation, respectively. This concept proved to be very successful for the HULIS samples in the saturation range from RHs larger than 98% up to activation. It was also shown to work well with data on HULIS taken from literature. Here, different atmospheric life-times and/or different sources for the different samples showed up in different coefficients for the parameterization. However, the parameterization did not work out well for the Aerosol-Water-Extract.
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We describe observations of atmospheric reactive nitrogen compounds including NO, NO<sub>2</sub>, total peroxy nitrates, total alkyl nitrates, and HNO<sub>3</sub> and their correlation with temperature. The measurements were made at a rural location 1315 m a.s.l. on the western slope of the Sierra Nevada Mountains in California during summer of 2001. The ratio of HNO<sub>3</sub> to its source molecule, NO<sub>2</sub>, and the ratio of HNO<sub>3</sub> to all other higher oxides of nitrogen (NO<sub>z</sub>) both increase with increasing temperature. Analysis of these increases suggests they are due to a steep increase in OH of between a factor of 2 and 3 over the range 18–32°C. Total peroxy nitrates decrease and total alkyl nitrates increase over the same temperature range. The decrease in the total peroxy nitrates is shown to be much less than expected if the rate of thermal decomposition were the sole important factor. This observation is consistent with the increase in OH inferred from the temperature trends in the HNO<sub>3</sub>/NO<sub>2</sub> ratio.
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Aerosol products by AERONET sun-sky radiometer measurements combined with air-mass backtrajectories were analyzed to identify source regions and pathways of air masses carrying aerosols to south-east Italy, and to determine the dependence of aerosol mean optical properties on advection patterns. Aerosol optical depth (AOD), fine mode fraction (η ), single scattering albedo (SSA), asymmetry factor (<i>g</i>), and lidar ratio (<i>Lr</i>) at 440 nm were used to characterize aerosol properties. The analysis of 5-day-backtrajectories ending in Lecce on south-east Italy and referring to 240 measurement days of the 2003–2004 years revealed that 32% of the measurement days were characterized by air masses coming from all continental European sources with the exception of Spain. 3% of the measurement days were characterized by air masses coming from both the Southern Mediterranean Sea and the Africa continent, and the Western Mediterranean, the Iberian Peninsula, and the Atlantic Ocean. 62% of the measurement days were characterized by mixed advection patterns. We found that AOD, SSA and <i>g</i> average values were not significantly dependent on air mass source regions. In contrast, η and <i>Lr</i> average values were quite affected by the air mass source region. AOD, &eta, SSA, <i>g</i>, and <i>Lr</i> average values, which were equal to 0.29±0.15, 0.93±0.03, 0.93±0.03, 0.67±0.03, and 72±20 sr, respectively indicated that the aerosol advected from all continental European sources with the exception of Spain, could be considered representative of "continental average aerosol", mostly made of water soluble and a small amount of soot and insoluble components. Polluted-desert dust particles characterized by AOD=0.29±0.05, η=0.72±0.05, SSA=0.94±0.03, <i>g</i>=0.69±0.02, <i>Lr</i>=56±13 sr, were advected over south-east Italy from the Southern Mediterranean Sea and the Africa continent. The Western Mediterranean, the Iberian Peninsula, and the Atlantic Ocean were instead responsible of the advection of maritime-polluted particles, which were characterized by AOD=0.27±0.17, η=0.8±0.1, SSA=0.94±0.03, <i>g</i>=0.67±0.03, <i>Lr</i>=58±24 sr. Hence, we found that the aerosol load over south-east Italy was dominated by moderately-absorbing, fine-mode particles even if it was also affected by the minor contribution of desert and maritime type aerosol. The application of an aerosol mask to the data points retrieved on measurement days characterized by mixed advection patterns, supported last comment
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Chemical ozone loss in winter 1991–1992 is recalculated based on observations of the HALOE satellite instrument, Version 19, ER-2 aircraft measurements and balloon data. HALOE satellite observations are shown to be reliable in the lower stratosphere below 400 K, at altitudes where the measurements are most likely disturbed by the enhanced sulfate aerosol loading, as a result of the Mt.~Pinatubo eruption in June 1991. Significant chemical ozone loss (13–17 DU) is observed below 380 K from Kiruna balloon observations and HALOE satellite data between December 1991 and March 1992. For the two winters after the Mt. Pinatubo eruption, HALOE satellite observations show a stronger extent of chemical ozone loss towards lower altitudes compared to other Arctic winters between 1991 and 2003. In spite of already occurring deactivation of chlorine in March 1992, MIPAS-B and LPMA balloon observations indicate that chlorine was still activated at lower altitudes, consistent with observed chemical ozone loss occurring between February and March and April. Large chemical ozone loss of more than 70 DU in the Arctic winter 1991–1992 as calculated in earlier studies is corroborated here.
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Vegetation fires have been acknowledged as an environmental process of global scale, which affects the chemical composition of the troposphere, and has profound ecological and climatic impacts. However, considerable uncertainty remains, especially concerning intra and inter-annual variability of fire incidence. The main goals of our global-scale study were to characterise spatial-temporal patterns of fire activity, to identify broad geographical areas with similar vegetation fire dynamics, and to analyse the relationship between fire activity and the El Niño-Southern Oscillation. This study relies on 10 years (mid 1996–mid 2006) of screened European Space Agency World Fire Atlas (WFA) data, obtained from Along Track Scanning Radiometer (ATSR) and Advanced ATSR (AATSR) imagery. Empirical Orthogonal Function analysis was used to reduce the dimensionality of the dataset. Regions of homogeneous fire dynamics were identified with cluster analysis, and interpreted based on their eco-climatic characteristics. The impact of 1997–1998 El Niño is clearly dominant over the study period, causing increased fire activity in a variety of regions and ecosystems, with variable timing. Overall, this study provides the first global decadal assessment of spatial-temporal fire variability and confirms the usefulness of the screened WFA for global fire ecoclimatology research.
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Emerging microwave satellite techniques are expected to provide improved global measurements of cloud ice mass. CloudSat, Aura MLS and Odin-SMR fall into this category and early cloud ice retrievals from these instruments are compared. The comparison follows the SMR retrieval product and is made for partial ice water columns above 12 km. None of the retrievals shows a significant degree of false cloud detections, the ratio between local mean values from the instruments is fairly constant and a consistent view of the geographical distribution of cloud ice is obtained. However, important differences on the absolute levels exist, where the overall mean is 9.6, 4.2 and 3.7 g m<sup>−2</sup> for CloudSat, SMR and MLS, respectively. Assumptions about the particle size distribution (PSD) are a consideration for all three instruments and constitute the dominating retrieval uncertainty for CloudSat. The mean for CloudSat when applying the same PSD as for MLS and SMR was estimated to 6.3 g m<sup>−2</sup>. A second main consideration for MLS and SMR are the effects caused by the poorer spatial resolution: a possible vertical misplacement of retrieved values and an impact of cloud inhomogeneities. The latter effect was found to be the dominating retrieval uncertainty for SMR, giving a possible mean value range of 2.3–8.9 g m<sup>−2</sup>. The comparison indicates a common retrieval accuracy in the order of 70%. Already this number should suffice for improved validations of cloud ice parametrisation schemes in atmospheric models, but a substantially better consistency between the datasets should be attainable through an increased understanding of main retrieval error sources.
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During past MANTRA campaigns, ground-based measurements of several long-lived chemical species have revealed quasi-periodic fluctuations on time scales of several days. These fluctuations could confound efforts to detect long-term trends from MANTRA, and need to be understood and accounted for. Using the Canadian Middle Atmosphere Model, we investigate the role of dynamical variability in the late summer stratosphere due to normal mode Rossby waves and the impact of this variability on fluctuations in chemical species. Zonal wavenumber 1, westward travelling waves are considered with average periods of 5, 10 and 16 days. Time-lagged correlations between the temperature and nitrous oxide, methane and ozone fields are calculated in order to assess the possible impact of these waves on the chemical species. Using Fourier-wavelet decomposition and correlating the fluctuations between the temperature and chemical fields, we determine that variations in the chemical species are well-correlated with the 5- and 10-day waves between 30 and 60 km, although the nature of the correlations depend strongly on altitude. Interannual variability of the waves is also examined.
